Methods for applying photographic images or designs to ceramic objects



March 2, 1965 CHARLES YU 3,171,742

METHODS FOR APPLYING PHOTOGRAPHIC IMAGES OR DESIGNS TO CERAMIC OBJECTS Filed July 23, 1959 Ffa] ENTOR C /1 cfr/e5 Vu ATTORNEY United States Patent O 3,171,742 METHODS FOR APPLYING PHGTOGRAPI-HC lil/XAGES R DESiGNS T0 CERl/IIC BSECTS Charles Yu, 70 Trinity St., Newton, NJ. Filed July 23, 1959, Ser. No. 828,986 7 Claims. (Cl. 965-34) Generically, my invention relates to ceramics and particularly to an improved method for applying photo- Igraphit: images or designs to ceramic objects, such as china, pottery or porcelain, Whenever used hereinafter the term ceramic biscuit or green ware, it is intended to mean ceramic clay bodies which have been once fired.

Briefly describedY my method can be employed in the application of photographic images or designs to ceramic objects in three ways:

(l) By direct coating of silver halide photographic emulsion to ceramic ware which has been fired once. The silver image is formed through photographic procedures; that is, exposure, development and fixing.

(A) Toning the image with ceramic pigments.

(B) Toning and intensification combination, in one of my formula toning involving intensification; chemical reactions both take place.

(C) Intensification of the image.

(D) Glazing and firing the ceramic ware carrying the image.

My invention comprehends the production of permanent color images or designs on ceramic Ware by the employment of light sensitive silver halide emulsions. This emulsion is essentially a hydrophilic colloid containing silver halide and a binder as protective colloid such as gelati-ne, polyvinyl alcohol, etc. The emulsion, as is well known in the art of the photographic industry is prepared with precipitation of silver nitrate or an alkali bromide, potassium or ammonium bromide, chloride, iodide, or chlorobromide or a mixture of all in gelatinous solution. The emulsion I apply to the ceramic ware can be used of the neutral, acid, or ammoniacal type, and the methods of utilizing the emulsion is described hereinafter.

Among the objects of my invention are improved methods for applying photographic images or designs to ceramic objects, with results which I have found to be manifestly superior to photographic images or designs on ceramic Ware heretofore accomplished producing with my invention true photographic reproductions in continuous tone.

Hereinafter I describe examples of a preferred method illustrating my invention and in FIGS. 1 to 9 of the appended drawings I have schematically depicted in greatly exaggerated cross section the elements involved in the steps of this method, like reference characters referring to like elements throughout the several views.

(l) A ceramic biscuit 5, an object which has been once red (FIG. l), has a porous surface and to fill up the inerstices I apply a thin layer of known cellulose material as a priming coat 6 (FIG. 2), which is covered with a gelatinal substratum layer 7 (FIG. 3). One example of a cellulose priming coat is as follows:

Nitrocellulose g 10 Ethyl acetate cc 40 Butyl acetate cc 40 Xylol cc 120 g-- 10 Water cc 100 Chrome alum (2%) cc 5 ice Soak the gelatine in water for 30 minutes at 70 F., melt the gelatine in a hot Water bath at 140 F. Cool to 100 F. add the chrome alum and it is ready to use.

(2) The photosensitive silver halide emulsion 8, as for example, a hydrophilic colloid containing silver halide and a binder as a protective colloid such as gelatine, polyvinyl alcohol, etc., is coated directly on the surface of the primed and substratum coated ceramic biscuit (FIG. 4).

(3) The photosensitive silver halide emulsion is Subjected to conventional photographic procedures, namely, exposure to actinic radiations with a negative or transparency, development by chemical reduction (FIG. 5) of the exposed silver halide to metallic silver to form a visible image 9 which is fixed by dissolving and removing the unexposed silver halide from the emulsion. A silver image is thus first formed on the ceramic object.

(4) I apply chemical toning or intensification or combination of both one after the other (FIG. 6), and by means of this the silver image is partially or completely replaced by ceramic colorants, known as underglaze colors, such as nickel in a nickel toning solution, through chemical reaction. After such reaction is completed, the ceramic Ware carrying the excess of toning chemicals and Water soluble reaction byproduct can be rinsed With water. An insoluble nickel compound image 10 remains.

An example of a separate nickel toning solution I may employ is:

Nickelous nitrate 25 g.

Potassium citrate g.

Potassium ferricyanide l0 g.

Nitric acid 2.5 cc. (concentrated). Water 750 cc.

An example of an intensifying and toning combination formula I may employ is:

(A) Potassium ferricyanide g 1.5 Water cc 50 Acetic acid (glacial) cc 15 (B) Ammonium molybdate g 1.5 Water cc 50 Acetic acid (glacial) cc l5 Mix A to B just before use.

After intensification, the object is then as previously described, Washed with water.

(5) The surface is dried, and after drying, a layer of suitable clear glaze 11 (FIG` 7) is applied on top of the nickel ferricyanide image before firing to a temperature corresponding to the respective fusion point of ceramic glaze and colorants which may be between 760 F. and 2600 F. (FIG. 8). The silver image in my method is utilized only as a transitional medium, the permanent image 12 (FIG. 9) ,being finally produced as a result of the replacement of the silver by nickel oxide or a mixture of other metal oxides depending upon the type of chemical toning solution util-ized.

While I have referred specifically to such ceramic colorants as copper, chrome, iron, nickel, I intend the use of others such as iron chromate, rutile, etc` I reserve the right to make such changes and modifications as may come within the scope of the appended claims.

l claim:

1. The method of producing pictures on a ceramic object which has been fired once and which has a porous surface, including the steps of (a) filling in the interstices in said surface with a priming coat (b) covering the coated surface with a hydrophilic gelatinal substratum layer n i (c) coating the primed and substraturn layered object with photosensitive silver halide emulsion (d) exposing the emulsion to actinic radiation to prosilver image is oxidized into silver compound, which silver compound is in turn replaced by an insoluble ceramic pigment compound (h) covering the surface with a glaze (i) ring the object a second time whereby a true photographic reproduction in continuons tone is produced. Y

2. The method of producing pictures on a ceramic object which has been once red and which has a porous surface, including the steps of (a) applying a priming coat of material adapted to ll the interstices (b) covering the coated surface with a hydrophilic gelatinal substratum layer (c) coating the primed and substratum layered object with an emulsion of a photosensitive silver halide in `gelatine colloid (d) exposing the emulsion to actinic radiation to produce a latent image (e) developing by chemical reduction of the exposed silver halide emulsion to metallic silver to form a visible image (f) iixing the silver image on the object by dissolving and removing the unexposed silver halide from the emulsion (g) treating the silver image with a chemical solution containing soluble heavy metallic compounds, whereby the silver image is oxidized into silver compound to which is then added insoluble heavy metallic compounds (h) covering the surface with a glaze (i) firing the object Va second time whereby a true photographic reproduction in continuous tone is produced. V

3. The method of producing permanent color pictures on a ceramic object which has been once fired and which has a porous surface, including the steps of:

(a) applying a priming coat of material adapted to iill the interstices (b) covering the coated surface with a hydrophilic gelatinal substratum layer (c) coating the primed and substratum layered object with an emulsion of'a photosensitive silver halide in `gelatine colloid (d) exposing the emulsion to actinic radiation to produce a latent image K (e) developing by chemical reduction of the exposed silver halide emulsion to metallic silver to form a visible image (f) fixing the silver image on the object by dissolving and removing the unexposed silver halide from the emulsion (g) treating the silver image with a ceramic colorant chemical solution containing soluble heavy metallic compounds, whereby the silver image is oxidized into silver compound to which Iis then added insoluble heavy metallic compounds A (h) covering the surface with a glaze (i) firing the object a second time whereby a true photographic reproduction in continuous tone is produced. 4. The method of producing pictures on ceramicobjects as described in claim 3 in which a primary coating includes:

Nitrocellulose g 10 Ethyl acetate cc 40 Butyl acetate cc 40 Xylol cc 120 5. The method of producing pictures on ceramic objects as described in claim 3 in which a formula for the substratumcovering the primed surface follows:

Gelatine g 10 Water cc Chrome alum (2%) cc 5 6. In a method of producing a photographic image on a ceramic object which has been fired once, including the steps of:

(a) priming the surface (b) coating the surface with a substratum hydrophilic gelatin layer (c) coating the object with a light sensitive photographic emulsion of the silver halide type (d) forming a visible image by:

(d1) exposure to actinic radiation to produce a latent image (d2) development by chemical reduction of the exposed silver halide to metallic silver (e) fixing the visible image by dissolving and removing the unexposed silver halide from the emulsion by a chemical solution known as silver halide solvent (f) intensifying vand toning the silver image by oxidation of said silver image by the application of a chemical solution containing soluble heavy metallic components known as underglaze colors V( g) covering the surface with a glaze (h) firing the object a second time. 7. A method of producing a photographic image on a ceramic object as described in claim 6 in which the chemical solution comprises nickelous nitrate, potassium citrate, potassium ferricyanide, nitric acid and water.

References Cited by the Examiner Photo Ceramics, Basic Processes and Formulas, Ceramic Industry, February 1946, pp. 54-55, 96-34.

Wall: The History of Three-Color Photography, 1925, American Photographic Pub. Co., Boston, Mass., pp. 399-401.

5 i yNom/.IAN G. ToRCHrN, Primary Examiner.

MILTON STERMAN. Bruin. E. MANGAN,

. Examiners. 

1. THE METHOD OF PRODUCING PICTURES ON A CERAMIC OBJECT WHICH HAS BEEN FIRED ONCE AND WHICH HAS A POROUS SURFACE, INCLUDING THE STEPS OF: (A) FILLING IN THE INTERSTICES IN SAID SURFACE WITH A PRIMING COAT (B) COVERING THE COATED SURFACE WITH A HYDROPHILIC GELATINAL SUBSTRATUM LAYER (C) COATING THE PRIMED AND SUBSTRATUM LAYERED OBJECT WITH PHOTOSENSITIVE SILVER HALIDE EMULSION (D) EXPOSING THE EMULSION TO ACTINIC RADIATION TO PRODUCE A LATENT IMAGE (E) DEVELOPING BY CHEMICAL REDUCTION OF THE EXPOSED SILVER HALIDE EMULSION TO METALLIC SILVER TO FORM A VISIBLE IMAGE (F) FIXING THE SILVER IMAGE ON THE OBJECT BY DISSOLVING AND REMOVING THE UNEXPOSED SILVER HALIDE FROM THE EMULSION (G) TREATING THE SILVER IMAGE WITH A SOLUTION CONTAINING SOLUBLE HEAVY METALLIC COMPOUNDS, WHEREBY THE SILVER IMAGE IS OXIDIZED INTO SILVER COMPOUND, WHICH SILVER COMPOUND IS IN TURN REPLACED BY AN INSOLUBLE CERAMIC PIGMENT COMPOUND (H) COVERING THE SURFACE WITH A GLAZE (I) FIRING THE OBJECT A SECOND TIME WHEREBY A TRUE PHOTOGRAPHIC REPRODUCTION IN CONTINUOUS TONE IS PRODUCED. 